CHEMICAL EQUILIBRIUM

What Is Chemical Equilibrium?

Chemical equilibrium refers to the state of a system in which the concentration of the reactant
and the concentration of the products do not change with time, and the system does not display
any further change in properties.

When the rate of the forward reaction is equal to the rate of the reverse reaction, the state of
chemical equilibrium is achieved by the system.

When there is no further change in the concentrations of the reactants and the products due to the
equal rates of the forward and reverse reactions, the system is said to be in a state of dynamic
equilibrium.

State of Chemical Equilibrium

A graph with the concentration on the y-axis and time on the x-axis can be plotted. Once the
concentration of both the reactants and the products stops showing change, chemical equilibrium
is achieved.

Why Is Chemical Equilibrium Called Dynamic Equilibrium?

The stage at which the rate of the forward reaction is equal to the rate of the backward reaction is
called an equilibrium stage.

At this point, the number of reactant molecules converting into products and product molecules
into reactants is the same.

The same equilibrium can be carried out with the same reactants anywhere with similar
conditions with continuous interchanging of molecules, and hence chemical equilibrium is
dynamic.

EQUILIBRIUM

There are two types of chemical equilibrium:

 Homogeneous Equilibrium
 Heterogeneous Equilibrium

HOMOGENOUS CHEMICAL EQUILIBRIUM

In this type, the reactants and the products of chemical equilibrium are all in the same phase.

Homogenous equilibrium can be further divided into two types:

Reactions in which the number of molecules of the products is equal to the number of molecules
of the reactants. For example,

 H2 (g) + I2 (g) ⇌ 2HI (g)

 N2 (g) + O2 (g) ⇌ 2NO (g)

Reactions in which the number of molecules of the products is not equal to the total number of
reactant molecules. For example,

 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

 COCl2 (g) ⇌ CO (g) + Cl2 (g)
HETEROGENEOUS CHEMICAL EQUILIBRIUM

In this type, the reactants and the products of chemical equilibrium are present in different
phases. A few examples of heterogeneous equilibrium are given below:

 CO2 (g) + C (s) ⇌ 2CO (g)

 CaCO3 (s) ⇌ CaO (s) + CO2 (g)

Thus, the different types of chemical equilibrium are based on the phase of the reactants and
products.

FACTORS AFFECTING CHEMICAL EQUILIBRIUM

According to Le-Chatelier’s principle, if there is any change in the factors affecting the
equilibrium conditions, the system will counteract or reduce the effect of the overall
transformation. This principle applies to both chemical and physical equilibrium.

There are several factors like temperature, pressure and concentration of the system that affect
equilibrium. Some important factors affecting chemical equilibrium are explained below.

Change in Concentration
  The concentration of the reactants or products added is relieved by the reaction, which
consumes the substance that is added.
 The concentration of reactants or products removed is relieved by the reaction, which is
in the direction that replenishes the substance which is removed.
 When the concentration of the reactant or product is changed, there is a change in the
composition of the mixture in chemical equilibrium.

Change in Pressure

 Change in pressure happens due to the change in the volume.

 If there is a change in pressure, it can affect the gaseous reaction as the total number of
gaseous reactants and products are now different.
 According to Le Chatelier’s principle, in heterogeneous chemical equilibrium, the change
of pressure in both liquids and solids can be ignored because the volume is independent
of pressure.

Change in Temperature

 The effect of temperature on chemical equilibrium depends upon the sign of ΔH of the
reaction and follows Le-Chatelier’s Principle.
 As temperature increases, the equilibrium constant of an exothermic reaction decreases.
 In an endothermic reaction, the equilibrium constant increases with an increase in
temperature.
 Along with the equilibrium constant, the rate of reaction is also affected by the change in
temperature.
 As per Le Chatelier’s principle, the equilibrium shifts towards the reactant side when the
temperature increases in the case of exothermic reactions; for endothermic reactions, the
equilibrium shifts towards the product side with an increase in temperature.

Effect of a Catalyst

 A catalyst does not affect the chemical equilibrium, it only speeds up a reaction.
 In fact, the catalyst equally speeds up the forward as well as the reverse reaction.
  This results in the reaction reaching its equilibrium faster.
 The same amount of reactants and products will be present at equilibrium in a catalysed
or non-catalysed reaction.
 The presence of a catalyst only facilitates the reaction to proceed through a lower-energy
transition state of reactants to products.

Effect of Addition of an Inert Gas

 When an inert gas like argon is added to a constant volume, it does not take part in the
reaction, so the equilibrium remains undisturbed.
 If the gas added is a reactant or product involved in the reaction, then the reaction
quotient will change.

Importance of Chemical Equilibrium

It is useful in many industrial processes, like

 Preparation of ammonia by Haber’s process: In this process, nitrogen combines with

hydrogen to form ammonia; the yield of ammonia is more at low temperature, high
pressure and in the presence of iron as a catalyst.
 Preparation of sulphuric acid by contact process: In this process, the fundamental
reaction is the oxidation of sulphur dioxide into sulphur trioxide. This involves chemical
equilibrium.

LAW OF MASS ACTION

What is the Law of Mass Action?

The law of mass action states that the rate of a reaction is proportional to the product of the
concentrations of each reactant.

This law can be used to explain the behavior exhibited by solutions in dynamic equilibria.

The law of mass action also suggests that the ratio of the reactant concentration and the product
concentration is constant at a state of chemical equilibrium.
The Equilibrium Constant (Kc)

The concentration of reactants and products, at equilibrium, are constant at a given temperature.
Consider the following simple reversible reaction where A & B are the reactants whereas C & D
are the products.

A+B⇌C+D

A mixture of products and reactants in a state of chemical equilibrium is known as an

equilibrium mixture. There exists a relation between the concentration of products and the
concentration of reactants for an equilibrium mixture. This relation can be equated as follows.

Here, Kc is called the equilibrium constant.

In this equation, the concentration of A at equilibrium is represented as [A] (similarly for B, C,

and D), and the stoichiometric coefficients of the reactants and products are 1.

It has been experimentally observed that the equilibrium constant is also dependent on the
stoichiometric coefficients of the reactants and products.

Therefore, the law of mass action dictates that the equilibrium constant, at a given constant
temperature, is equal to the product of the concentration of products raised to the respective
stoichiometric coefficients divided by the product of the reactant concentrations, each raised to
the corresponding stoichiometric coefficient.

This is also known as the equilibrium law or the law of chemical equilibrium.

Representation of the Equilibrium Constant

For a balanced reaction of the type,

aA + bB ⇌ cC + dD
According to the law of mass action, the constant value obtained by relating equilibrium
concentrations of reactants and products is called the equilibrium constant. For the forward
reaction, this is given by

The equilibrium constant for the reverse reaction is the inverse of the forward reaction and is
given by:

Problems on Chemical Equilibrium

Given the equation, N2 (g) + 3H2 (aq) ⇌ 2NH3 (g). Find Q and determine which direction
the reaction will shift in order to reach the state of chemical equilibrium.

Solution:

Given, [N2] = 0.04M, [H2] = 0.09M, and K = 0.040

Since only nitrogen and hydrogen concentration is given, they can be assumed as the reactants
and ammonia as the product. Since ammonia concentration is not given, it can be assumed to be
zero.

As q is the ratio of the relative concentration of products to reactants, here, Q =0.

Since K = 0.04 is larger than Q, nitrogen and hydrogen will combine to form the product
ammonia.

Units of Equilibrium Constant

The equilibrium constant is the ratio of the concentrations raised to the stoichiometric
coefficients. Therefore, the unit of the equilibrium constant = [Mole L-1]△n.
Where, ∆n = sum of stoichiometric coefficients of products – sum of stoichiometric coefficients
of reactants.

Equilibrium Constant, Reaction Quotient and Gibbs Free Energy

K is the ratio of the relative amount of products to reactants at equilibrium, while Q is the ratio at
any point in time of the reaction. The Q value can be compared to K to determine the direction of
the reaction to take place. The spontaneity of the process is related to the free energy change. △G
(Gibbs Free Energy), K (Equilibrium Constant), and Q (Reaction Quotient) are related, as
detailed below:

1. △G < 0 and Qc ˂ Kc or Kp at the start of the reaction: The reaction will proceed to
form products.

2. △G = 0 and Qc = Kc or Kp at equilibrium, and no more changes in the concentration

of the mixture.

3. △G > 0 and Qc > Kc or Kp after equilibrium: The reaction will proceed in the
direction to form reactants.

Equilibrium Constant vs Reaction Quotient

 Kc = Equilibrium constant measured in moles per litre.

 Kp = Equilibrium constant calculated from the partial pressures
Characteristics of Equilibrium Constant

1. It is reaction specific, and at a constant temperature, it is fixed.

2. A catalyst changes the rate of forward and backward reactions equally, not to affect the
value of the equilibrium constant.
3. Changes in concentration, pressure, temperature, and inert gases may affect the
equilibrium, favouring either forward or backward reaction but not the equilibrium
constant.
4. It is related to the standard free energy as, △G0 = -RT ln Kequ.
5. For the same reversible reaction, Kequ has different values at different temperatures.
6. The equilibrium constant of the reverse equilibrium is the reciprocal of the original
equilibrium, i.e. Krev = 1/Kequ.
7. If the equilibrium reaction stoichiometry is changed, the power of the equilibrium
constant also gets changed by the same quantity.
8. If the equilibrium constant for the reaction, A + B ⇌ C + D, is K, then, for equilibrium
reaction 3A = 3B ⇒ 3C + 3D is K3.
9. In case the stepwise multiple equilibria lead to the final products, the equilibrium
constant of the net equilibrium = product of each stepwise equilibrium constant.
Therefore, the net equilibrium constant K = K1 × K2 × K3.
10. Simultaneous equilibrium reactions have a common product. The equilibrium constant of
the reactions does not change. Due to the higher concentration of the common product,
the product concentrations will be reduced.

Applications of Equilibrium Constant

Equilibrium Constant for Predicting the Extent of Reaction

The equilibrium constant (Kc) can be used to predict the extent of a reaction, i.e. the degree of the
disappearance of the reactants. The magnitude of the equilibrium constant gives an idea of the
relative amount of the reactants and the products.
Case 1: The larger value of the equilibrium constant (>103) shows that forward reaction is
favoured, i.e. the concentration of products is much larger than that of the reactants at
equilibrium.

For example,

 H2(g) + Br2(g)⇌ 2HBr(g) ⇒ Kc = 5.4×1018

 H2(g) + Cl2(g)⇌ 2HCl(g) ⇒ Kc = 4×1031
 H2(g) + 12O2(g) ⇌ H2O(g) ⇒ Kc = 2.4×1047

This shows that at equilibrium, the concentration of the products is very high, i.e. reaction goes
almost to completion.

Case 2: Intermediate value of the equilibrium constant (10-3 to 103) show that the concentration
of the reactants and products are comparable.

For example,

 Fe3 (aq) + SCN (aq) ⇌ [Fe(SCN)]2 (aq) ⇒ Kc = 138 at 298 K

 H2 (g) + I2 (g) ⇌ 2HI (g) ⇒ Kc = 57 at 700 K.

Case 3: Low value of equilibrium constant (<10-3) shows that backward reaction is favoured, i.e.
concentration of reactants is much larger than that of products, i.e. the reaction proceeds to a
very small extent in the forward direction.

For example,

 N2 (g) + O2 (g) ⇌ 2NO (g) ⇒ Kc =4.8 × 10-31 at 298K

 H2O (g) ⇌ H2 (g) + (1/2) O2 (g) ⇒ Kc = 4.1 × 10-48

Equilibrium Constant for Predicting the Direction of a Reaction

The equilibrium constant can be used to predict the direction of the reaction. We need a term,
reaction quotient (Qc expressed in terms of concentrations or Qp in terms of partial pressures)
similar to the equilibrium constant, except that the conditions are not at equilibrium.
For a balanced reaction, aA + bB ⇌ cC + dD

The reaction quotient (Qc or Qp) is given as:

Qc = [C]c[D]d/[A]a[B]b

Qp = pcC × pdD / paA × pbB

Comparison with Kc and the direction of reaction:

 If Q = Kc, the reaction is in equilibrium [Where, Kc = equilibrium constant]

 If Q > Kc, Q tends to decrease so as to become equal to K, the reaction will proceed in the
backward direction.
 If Q < Kc, Q tends to increase so as to become equal to K, the reaction will proceed in the
forward direction.

When factors like concentration, pressure, temperature, and inert gases that affect
equilibrium are changed, the equilibrium will shift in that direction, where the effects caused by
these changes are nullified.

Le Chatelier’s principles are often used to manipulate reversible reactions in order to obtain
suitable outcomes (such as an improvement in yield).

Effect of Concentration Changes on Equilibrium and Product Formation

As per Le Chatelier’s principles, the only way for equilibrium to accept more reactants is to
increase product formation. The forward reaction is favoured when the concentration of the
reactant is increased. The equilibrium of the reaction shift towards the use of reactants in the
reaction, which decreases the concentration of the reactants.

Similarly, the addition of product (concentration/pressure) shall increase the backward reaction
to decrease the product concentration. The backward reaction is favoured when the concentration
of the reactant decreases, the equilibrium of the reaction shift towards the production of
reactants, and the concentration of the reactants is more.
Example:

Consider a reaction between oxygen and sulfur dioxide to produce sulfur trioxide.

2SO2(g) + O2(g) ⇋ 2SO3(g)

If the concentration of the reactant increases, then

 Equilibrium will shift towards the decrease in the concentration of the reactants.
 More favoured for the forward reaction.
 Some of the SO2 or O2 form SO3.
 Equilibrium of the reaction shift towards the right.

If the concentration of the reactant decreases, then

 Equilibrium will shift towards the increase in the concentration of the reactants.
 More favoured for the backward reaction.
 Some of the SO3 would change to SO2 or O2.
 Equilibrium of the reaction shift towards the left.

If the product decreases, then

 The equilibrium of the reaction shift to increase the concentration of the sulfur trioxide.
 Increase in the forward reaction rate.
 Some of the SO2 or O2 form SO3.
 Equilibrium of the reaction shift towards the right.

If the product increases, then

 The equilibrium of the reaction shifts to decrease the concentration of the sulfur trioxide.
 Increase in the reverse reaction rate.
 Some of the SO3 would change to SO2 or O2.
 Equilibrium of the reaction shift towards the left.
Effect of Change of Volume, Pressure, or Inert Gas on Equilibrium and Product
Formation

Kp = Kc (RT)Δn = Kc (p/v)Δn

Change of volume, pressure or inert gases has no effect on the reactions of liquids and solids.
They may have an effect in gaseous reactions, and that too, only when the difference in the sum
of the number of reactant and product molecules (∆n) is not zero.

When ∆n = 0:

As per Le Chatelier’s principles, there will be no effect on Equilibrium and Product

Formation by changing the volume, pressure or inert gas.

When ∆n = +ve:

An increase in pressure or decrease in volume will decrease the formation of the product. A
decrease in pressure or increase in volume shall have the opposite effect of increasing the
product formation.

Inert gases do not take part in the reaction and shall increase the volume or pressure only.

 At constant pressure, the addition of inert gas increases the volume, so it increases the
product formation.
 At constant volume, inert gas is added, which does not take part in the reaction; the
equilibrium remains undisturbed because the addition of inert gas at constant volume
does not change the partial pressures or the molar concentrations of the substance
involved in the reaction. The reaction quotient changes only if the added gas is a reactant
or product involved in the reaction.

PCl5 ⇌ PCl3 + PCl2

In the decomposition of phosphorus pentachloride ∆n = +1.

An increase in pressure or decrease in volume decreases the decomposition of PCl5

  At constant pressure, the addition of inert gas increases the PCl5 formation.
 At constant volume, the addition of inert gas decreases the PCl5 formation.

When ∆n = -ve:

As per Le Chatelier’s principle, an increase in pressure or decrease in volume will increase the
formation of the product.

At constant pressure, the addition of inert gas increases the volume, so it decreases the product
formation.

 At constant volume, the equilibrium remains undisturbed. It is because adding an inert

gas at constant volume does not change the partial pressures or the molar concentrations
of the substance involved in the reaction. The reaction quotient changes only if the added
gas is a reactant or product involved in the reaction.

N2 + 3H2 ⇌ 2NH3

In the formation of ammonia, ∆n = -2. The increase of pressure or decrease in volume increases
the formation of ammonia.

 At constant pressure, the addition of inert gas decreases ammonia formation.

 At constant volume, the addition of inert gas increases ammonia formation

Effect of Change of Temperature on Equilibrium and Product Formation

The individual reaction in the equilibrium can be either endothermic or exothermic. Likewise, at
equilibrium, the net energy involved may make the reversible reactions either endothermic or
exothermic.

According to Le Chatelier’s Principles,

 In exothermic equilibrium, an increase in temperature decreases product formation, and a

decrease in temperature increases product formation.
  In endothermic reactions, an increase in temperature increases the product formation, and
a decrease in temperature decreases the product formation

Le Chatelier’s Principle on Change of Temperature

As per the Van’t Hoff equation, for an exothermic equilibrium, ∆H will be negative. An increase
in temperature shall decrease K2, or a decrease in temperature increases K2. The opposite is true
for an endothermic reaction.

Example:

Consider a reaction

N2(g)+ 3H2(g) ⇋ 2NH3(g) ΔH=−92kJ

Increase in temperature

 This prefers an endothermic reaction because it takes energy.

 An endothermic reaction is a reverse reaction, and it is favoured.
 The yield of the product (NH3) decreases.

Decrease in temperature

 This prefers an exothermic reaction because it gives energy.

 An exothermic reaction is a forward reaction, and it is favoured.
 The yield of the product (NH3) increases.

Effect of Catalyst on Equilibrium and Product Formation

A catalyst is a substance that changes the rate of reactions (increase or decrease) without
quantitatively taking part in the reaction.

In a reversible reaction, the change in reaction rate is the same for both forward and backward
reactions.

The ratio of the reaction rates remains the same, and so is the equilibrium constant. According to
Le Chatelier’s principles, the presence of the catalyst may speed up or delay the attainment of
equilibrium but will not affect the equilibrium concentration.

Frequently Asked Questions (FAQs)

Q1

What happens to the COBr2 ⇌ CO+ Br2 reaction on adding inert argon gas?

There will be no change in the reaction, and the reaction will be in equilibrium.
Q2

What happens when the temperature is decreased in the following reaction 2H2 + O2 →
2H2O?

The forward reaction is favoured.

Q3

What happens if we add hydrogen to the following reaction- N2 + 3H2 → 2NH3?

In order to be in equilibrium, the reaction shifts towards the product.

Kc Calculations

Calculating a Value for the Equilibrium Constant Kc

If you know the values of the molar concentration of each of the substances at equilibrium, you
can calculate the value of Kc by substituting the concentrations into the expression above. You
will need to work out the units yourself as these will vary per calculation.

Practice Question: What is the value for Kc of the reaction with the equation:

H2 (g) + Cl2 (g) ⇌ 2HCl (g)? The equilibrium concentrations are: [H2] = 0.67 mol dm–3, [Cl2)
= 0.83 mol dm–3 and [HCl] = 0.33 mol dm–3.

Method:

1. Write an expression for Kc using the reversible reaction equation.

2. Substitute the molar equilibrium concentrations into the equation and calculate the
value of Kc.

3. Finally calculate the units of the value for Kc by just substituting the equation with the
units without putting the numbers in.
Therefore the units cancel out therefore there are no units for Kc in this example.

Finding the Equilibrium Concentrations

Sometimes you will have to calculate the equilibrium concentrations in a reaction before
calculating the value of Kc.

Practice Question: In an experiment, 0.18398 moles of carbon monoxide is hydrogenated with

0.22046 moles of hydrogen. The reaction takes place in a vessel of 1.00 dm3. The equilibrium
mixture contains 0.05176 moles of methanol. The equation is: CO(g) + 2H2(g) ⇌ CH3OH(g).
What is the value of Kc including units?

Method:

1. Calculate the number of moles of CO and H2 at equilibrium.

We know that CO and CH3OH are in a 1:1 molar ratio. This means that for every 1 mole of CO
that reacts, 1 mole of CH3OH is produced.

Therefore as 0.051716 moles of CH3OH is produced, the number of moles of CO would have
reduced by 0.0 51716 moles.

Number of moles of CO at equilibrium = 0.18398 – 0.051716 = 0.132264 moles

We also know that H2 and CH3OH are in a 2:1 molar ratio. For every 1 moles of CH3OH
produced, 2 moles of H2 are used up.

This means that as 0.051716 moles of CH3OH is produced, the number of moles of H2 must
have reduced by 0.051716 moles multiplied by 2:

Number of moles of H2 at equilibrium 0.22046 – (0.051716 x 2) = 0.117028 moles

Calculations with Equilibrium

Constants

2. Calculate the molar concentrations by dividing each number of moles by the total
volume of the vessel.

Here the equilibrium molar concentrations are the same as the equilibrium number of moles of
each of the substances as the volume of the vessel is 1.00 dm3.

When you divide each of the equilibrium number of moles by 1.00, you get the same value for
the concentration.

The molar concentrations at equilibrium are therefore:

[ CO ] = 0.132264 mol dm–3

[ H2 ] = 0.117028 mol dm–3
[ CH3OH ] = 0.051716 mol dm–3
3. Write an expression for Kc and substitute the concentrations into the Kc expression to
calculate its value.

4. Finally work out the units.

Therefore the units of Kc = mol dm–6

The value of Kc is 28.6 mol dm–6

Using Kc to find the Equilibrium Concentrations

If you know the value of Kc, you can calculate the concentrations of substances in a reaction at
equilibrium.

Practice Question: In an experiment that was allowed to reach equilibrium, 2.5 moldm–3 of
H2O and 3.0 mol dm–3 of CO are allowed to reach equilibrium. If the value of Kc is 4.5 at 800K
what are the equilibrium concentrations of all species in the equation: CO(g) + H2O(g) ⇌ H2 (g)
+ CO2 (g) ?
Method:

1. First of all write an expression for Kc using the reversible equation given.

2. Substitute all the known equilibrium concentrations into the Kc expression.

3. Finally rearrange the equation to find the unknown equilibrium concentrations.

[H2] [CO2] = 4.5 x 7.5 = 33.75

We know that the molar ratio of [H2] : [CO2] is 1:1.

Therefore as [H2] = [CO2] = √33.75 = 5.81 mol dm–3 (to 3 significant figures).

Therefore the equilibrium concentrations of all species in the equation are:

[H2] = 5.81 mol dm–3

[CO2] = 5.81 mol dm–3
[CO] = 3.0 mol dm–3
[H2O] = 2.5 mol dm–3
Effect of Changes in Temperature, Concentration and Pressure on Kc

Temperature and Kc

The value of Kc will change if the temperature is changed as the temperature change will affect
the direction in which the reaction goes. Earlier we learned that an increase in temperature
favours the reaction in the endothermic reaction and a decrease in temperature favours the
reaction in the exothermic reaction.

If you change the temperature of a reaction, the change in Kc depends on what happens:

Increase in Product = ↑Kc

If we write an expression for Kc, remember that the concentrations of the products are at the top
(numerator) and the concentrations of the reactants are at the bottom (denominator). This means
that if a temperature change increases the amount of product that is formed, the value of the
numerator will increase and therefore the value of Kc will be higher.

Decrease in Product = ↓Kc

If a temperature change decreases the amount of product that is formed, the value of the
numerator will decrease and therefore the value of Kc will be lower.

Changed Concentration = Unchanged Kc

If the concentration of either the reactants or products is changed Kc is not changed.

Catalyst = Unchanged Kc
Using a catalyst in the reaction does not affect the value of Kc. A catalyst speeds up the reaction
in both directions so that equilibrium is reached faster